CN103172788B - Preparation method of dispersing agent - Google Patents
Preparation method of dispersing agent Download PDFInfo
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- CN103172788B CN103172788B CN201310100419.XA CN201310100419A CN103172788B CN 103172788 B CN103172788 B CN 103172788B CN 201310100419 A CN201310100419 A CN 201310100419A CN 103172788 B CN103172788 B CN 103172788B
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Abstract
The invention discloses a preparation method of a dispersing agent. The preparation method comprises the following steps of: carrying out free radical polymerization reaction onto a lipophilic monomer (A), a functional adsorption monomer (B), a hydrophilic monomer (C) and molecular weight regulator in a solvent after initiating by virtue of an initiator; removing the solvent after the free radical polymerization reaction is finished, adjusting the pH value to 7.0-10.0 by using inorganic alkali to prepare the dispersing agent. The dispersing agent, which is synthesized by the lipophilic monomer (A), the functional adsorption monomer (B) and the hydrophilic monomer (C), is insoluble in water, however, the dispersing agent can be converted into a salt form, so that the product has the advantages of good water-solubility, good dispersion and good dispersion stability.
Description
Technical field
The present invention relates to a kind of dispersion agent, be specifically related to a kind of preparation method of many anchor points macromolecule dispersing agent.
Background technology
Agricultural chemicals is that the mankind prevent and treat Crops Pests Control of Diseases Insects And Weeds Pests of Crops, improves crop yield and important means, plays a part very importantly in agriculture production, and tensio-active agent has indispensable vital role in Pesticide formulation, is described as " industrial monosodium glutamate ".For a long time, because the class of China's pesticide surfactant does not get a promotion, cause China's pesticide formulation still taking missible oil, wettable powder, pulvis and the large formulation of granule four as main.Now, along with more and more higher to the requirement of environment and safety performance, the pesticide formulation also present the trend of hydrotropismsization, high-content future development.In the last few years, the development of water-based pesticide formulation, particularly water suspending agent (SC), water dispersible granules (WG) was very rapid, had pollution-free, high content of dispersion, good dispersity, and the advantages such as complete processing maturation, have good market outlook.
Along with agricultural chemicals hydrotropismsization future development, must develop supporting its use of a series of New-type adjuvant.Dispersion agent is most important in pesticide preparation, is also a class tensio-active agent of consumption maximum, plays and stop former medicine particle to gather in pharmaceutical formulation, makes formulation of pesticide form a long stable dispersion homogeneous system, easy to use and raising drug effect.
At SC, in WG formulation, while using traditional dispersion agent as polycondensation naphthalenesulfonate, lignin sulfonate, alkylaryl sulphonate class, there is the problems such as dispersing property is undesirable, dispersion stabilization is poor, can not meet the requirement of formulation development.In the last few years, the development of agricultural high score subclass dispersion agent was very rapid, and because structure can be adjusted, molecular weight is controlled, therefore had the incomparable performance of traditional dispersion agent, was applied in the pesticide formulation, can reach desirable dispersion effect.Patent US11726200 and US2007/0244216 adopt SMA or PIBSA resin to prepare dispersion agent through Amino Terminated polyether(ATPE) modification, have good dispersing property, but Amino Terminated polyether(ATPE) only has fewer companies to produce, and cost is too high and buying is inconvenient.Patent US6339043 and US6855763 employing unsaturated acid (acid anhydrides) carry out polymerization with а-vinyl toluene class monomer and prepare dispersion agent, are the more than 2 times of conventional products but the dispersion agent of preparation adds cost in aq. type formula.Patent CN200710052016.7 discloses a kind of amphipathic graft copolymer dispersion agent, can be for aq. type formulation of pesticide, but need to adopt the method for catalytic chain transfer polymerization (CCTP), industrial production realizes difficulty at present.Patent CN200810201807.6 discloses dispersion agent prepared by a kind of rosin derivative and vinylformic acid, styrene sulfonic acid sodium polymerization, can be for G-30027 water dispersible granules, but the rosin derivative of setting forth preparation is complicated, is unfavorable for industrial production.The comb-shaped copolymer of patent CN200710025659.2 and CN200910157864.3 invention, in water suspending agent, there is good dispersing property and retention, but the dispersion agent side chain of synthesized is polyoxyethylene ether, though have good water-soluble, but molecule is easily wound around, and dispersion agent itself is difficult to be processed into pulvis, can only in formula, use with the form of its aqueous solution.
Summary of the invention
Technical problem to be solved by this invention is: the preparation method that a kind of macromolecule dispersing agent with many anchor points adsorption group is provided.
For solving the problems of the technologies described above, technical scheme of the present invention is: a kind of preparation method of dispersion agent, the steps include: under nitrogen atmosphere, lipophilicity monomer (A), functional absorption monomer (B), hydrophilic monomer (C) in corresponding solvent, carry out Raolical polymerizable after causing with molecular weight regulator by initiator; After Raolical polymerizable finishes, except desolventizing, regulate pH=7.0～10.0 with mineral alkali, make dispersion agent;
Further, its concrete steps are: in reactor, add solvent and initiator, N
2displacement 30 ± 10min, keep nitrogen atmosphere, reactor is warming up to 65～80 DEG C and keep this temperature of reaction, drip lipophilicity monomer (A), functional absorption monomer (B), the mixture of hydrophilic monomer (C) and molecular weight regulator composition, control time for adding is 3～6h, dropwise, keeping reactor temperature is 65～80 DEG C, stir 1 ± 0.5h, underpressure distillation is except desolventizing, in reactor, add mineral alkali again, in stirring and 1.5 ± 0.5h, control pH=7.0～10.0, prepare dispersion agent, now dispersion agent is thick liquid, further dispersion agent being made to the aqueous solution directly uses, or dispersion agent is made to white powder with micronizer mill.The weight-average molecular weight of described dispersion agent is 1000～40000g/mol, is preferably 6000～12000g/mol(weight-average molecular weight and regulates by the consumption of molecular weight regulator in polymerization process).
In the preparation process of described dispersion agent, monomer and initiator can adopt dropping, the disposable feed way that feeds intake to drop in reactor, and for fear of the generation of implode reaction, the present invention adopts the method for dropping to feed intake, monomer and initiator need drip respectively, immiscible.
Described lipophilicity monomer (A) is selected from least one in alicyclic ring same clan monomer, phenyl ring class monomer, heterocyclic vinyl monomer; In molecular structure, not only play the effect of lipophilicity anchoring group is provided, also make molecular structure there is rigidity, effectively prevent the upset of molecular structure by steric hindrance.
Described functional absorption monomer (B) is for having the vinyl monomer of ester group, morpholine group, pyridine groups or furan group; Functional absorption monomer (B) object is on the basis of the effective anchoring of (A) monomer, increases with agricultural chemicals surface and can produce the adsorption group of anchorage effect, thereby reach multi-point-anchoring effect, strengthens dispersiveness and dispersion stabilization.
The vinyl compound of described hydrophilic monomer (C) for containing acid, acid anhydrides or sulfonic acid group; Give the hydrophilicity that dispersant molecule is good, and can, by the ion from ionizing out, by electrostatic interaction, reach stable dispersion effect in the aqueous solution.
The total mass of described lipophilicity monomer (A) and functional absorption monomer (B) accounts for the 30-65% of lipophilicity monomer (A), functional absorption monomer (B), hydrophilic monomer (C) three monomer total mass;
Described hydrophilic monomer (C) quality used accounts for the 70%-35% of lipophilicity monomer (A), functional absorption monomer (B), hydrophilic monomer (C) three monomer total mass.
Described molecular weight regulator is mercaptoethanol, Thiovanic acid, alkyl sulfhydryl; Described molecular weight regulator consumption accounts for the 0.1%-1% of lipophilicity monomer (A), functional absorption monomer (B), hydrophilic monomer (C) three monomer total mass.
Described lipophilicity monomer (A) is selected from the one in following substances: vinyl pentamethylene, vinyl cyclohexane, vinyl naphthalene, vinylbenzene, а-vinyl toluene, limonene, norbornylene, beta-pinene.
One in the preferred following substances of described lipophilicity monomer (A): vinyl pentamethylene, vinyl cyclohexane, vinylbenzene, а-vinyl toluene, limonene, vinyl naphthalene.
Described functional absorption monomer (B) is selected from the one of following substances: methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, N-vinyl morpholine, vinyl pyridine.
Described hydrophilic monomer (C) is selected from the one of following substances: vinylformic acid, methacrylic acid, toxilic acid, maleic anhydride, fumaric acid, myristic acid, vinyl phosphoric acid, Sodium styrene sulfonate, sodium vinyl sulfonate.
Described hydrophilic monomer (C) is the one of following substances preferably: methacrylic acid, toxilic acid, maleic anhydride, vinyl phosphoric acid.
Described solvent is aromatic hydrocarbon solvent or ketones solvent (carry out in this type of solution in preparation process, can better control molecular weight and molecualr weight distribution).
Described ketones solvent is selected from the one in following solvents: acetone, butanone, methyl ethyl ketone, pimelinketone.Preferably ketones solvent, as the solvent of polyreaction, because ketone is stronger to the dissolving power of macromolecule dispersing agent, can effectively prevent that the precipitation of macromolecule dispersing agent in polymerization process from producing.
Described initiator is superoxide or azo compound; Described initiator quality used accounts for the 0.5%-3% of lipophilicity monomer (A), functional absorption monomer (B), hydrophilic monomer (C) three monomer total mass.
Described initiator is preferably H
2o
2, benzoyl peroxide (BPO), dilauroyl peroxide (LPO), peroxidized t-butyl perbenzoate (BPB), Diisopropyl azodicarboxylate (ABIN) or 2,2'-Azobis(2,4-dimethylvaleronitrile) (ABVN).
Described initiator is benzoyl peroxide (BPO), peroxidized t-butyl perbenzoate (BPB) or Diisopropyl azodicarboxylate (ABIN) more preferably.
Described mineral alkali is sodium hydroxide, potassium hydroxide or ammoniacal liquor.
Beneficial effect of the present invention:
The synthetic dispersion agent of described lipophilicity monomer (A), functional absorption monomer (B), hydrophilic monomer (C) itself is water insoluble, but by converting thereof into the form of salt, just product has good water-solublely, has good dispersiveness and dispersion stabilization simultaneously.Other Neutralizing modes, as with neutralizations such as thanomin, diethanolamine, trolamines, are unfavorable for the raising of dispersion agent dispersing property, are also unfavorable for that product is processed into powder simultaneously.
In process of production, slough solvent and carry out recycling by underpressure distillation, final dispersion agent finished product is owing to having good processing characteristics, can make its aqueous solution directly uses, also can carry out powder process by comminution by gas stream drying machine, obtain white powder finished product, be convenient to transport and use.
Brief description of the drawings
Fig. 1 is the preparation flow figure of dispersion agent.
Embodiment
Following examples are that the present invention is carried out to more detailed description, but the present invention are not produced to any restriction.
Embodiment 1
To with agitator, A constant pressure dropping groove (2Kg acetone solution 90g azo-bis-isobutyl cyanide, for subsequent use) and B constant pressure dropping groove (the a-vinyl toluene of 2.1kg, 0.3Kg butyl methacrylate, 3.0Kg toxilic acid, 30g lauryl mercaptan 5Kg acetone solution, for subsequent use), in the 20L enamel polymerization still of thermometer, condenser and solvent receptor, add 2.1Kg acetone and 0.6Kg toxilic acid, N
2replace after 30 minutes, be warming up to 65 DEG C, the valve of opening A, B two dropwise adding tanks slowly drips material to reactor, control 65～70 DEG C of temperature of reaction, after 5h, B dropwise adding tank material drips off, after 5.5h, A dropwise adding tank material drips off, after insulated and stirred 1h, underpressure distillation is also collected solvent acetone 8.5Kg, to adding in reactor in the 45%NaOH of 5.66Kg and 6.8Kg technique soft water and after 1.5h, send micronizer mill to pulverize to obtain white powder finished product, be labeled as Y-1, the weight-average molecular weight of surveying through GPC is 7890g/mol.
Embodiment 2
To with agitator, A constant pressure dropping groove, (2Kg butanone dissolves 120g azo two cyanogen in different heptan, for subsequent use) and B constant pressure dropping groove (vinylbenzene of 2.128kg, 0.912Kg N-vinyl morpholine, 2.50Kg maleic anhydride, 5Kg butanone dissolving for 18.2g lauryl mercaptan, for subsequent use), in the 20L enamel polymerization still of thermometer, condenser and solvent receptor, add 2.2Kg acetone and 0.54Kg maleic anhydride, N
2replace after 30 minutes, be warming up to 66 DEG C, the valve of opening A, B two dropwise adding tanks slowly drips material to reactor, control 65～70 DEG C of temperature of reaction, after 3.5h, B dropwise adding tank material drips off, after 4.0h, A dropwise adding tank material drips off, after insulated and stirred 1h, underpressure distillation is also collected solvent butanone 8.7Kg, to adding in reactor in the 45%NaOH of 5.58Kg and 7Kg technique soft water and after 1.5h, send micronizer mill to pulverize to obtain white powder finished product, be labeled as Y-2, the weight-average molecular weight of surveying through GPC is 11430g/mol.
Embodiment 3
To with agitator, A constant pressure dropping groove, (2Kg butanone dissolves 100g azo-bis-isobutyl cyanide, for subsequent use) and B constant pressure dropping groove (vinyl naphthalene of 1.5kg, 0.50Kg N-vinyl morpholine, 3.50Kg vinyl phosphoric acid, 5Kg butanone dissolving for 9.0g lauryl mercaptan, for subsequent use), in the 20L enamel polymerization still of thermometer, condenser and solvent receptor, add 2.0Kg acetone and 0.50Kg vinyl phosphoric acid, N
2replace after 30 minutes, be warming up to 75 DEG C, the valve of opening A, B two dropwise adding tanks slowly drips material to reactor, control 75～80 DEG C of temperature of reaction, after 4.0h, B dropwise adding tank material drips off, after 4.5h, A dropwise adding tank material drips off, after insulated and stirred 1h, underpressure distillation is also collected solvent butanone 8.7Kg, to adding in reactor in the 45%NaOH of 8.20Kg and 5.5Kg technique soft water and after 1.5h, send micronizer mill to pulverize to obtain white powder finished product, be labeled as Y-3, the weight-average molecular weight of surveying through GPC is 7860g/mol.
Embodiment 4
To with agitator, A constant pressure dropping groove, (2Kg butanone dissolves 152g benzoyl peroxide, for subsequent use) and B constant pressure dropping groove (the a-vinyl toluene of 2.50kg, 0.50Kg vinyl pyridine, 2.50Kg toxilic acid, 5Kg butanone dissolving for 10g lauryl mercaptan, for subsequent use), in the 20L enamel polymerization still of thermometer, condenser and solvent receptor, add 2.50Kg butanone and 0.6Kg toxilic acid, N
2replace after 30 minutes, be warming up to 70 DEG C, the valve of opening A, B two dropwise adding tanks slowly drips material to reactor, control 70～75 DEG C of temperature of reaction, after 3h, B dropwise adding tank material drips off, after 3.5h, A dropwise adding tank material drips off, after insulated and stirred 1h, underpressure distillation is also collected solvent acetone 8.8Kg, to adding in reactor in the 45%NaOH of 5.62Kg and 6.9Kg technique soft water and after 1.5h, send micronizer mill to pulverize to obtain white powder finished product, be labeled as Y-4, the weight-average molecular weight of surveying through GPC is 10087g/mol.
Embodiment 5
To with agitator, A constant pressure dropping groove, (2Kg butanone dissolves 170g azo two cyanogen in different heptan, for subsequent use) and B constant pressure dropping groove (limonene of 1.55kg, 0.50Kg butyl methacrylate, 3.55Kg methacrylic acid, 5Kg butanone dissolving for 62g lauryl mercaptan, for subsequent use), in the 20L enamel polymerization still of thermometer, condenser and solvent receptor, add 2.50Kg butanone and 0.60Kg methacrylic acid, N
2replace after 30 minutes, be warming up to 70 DEG C, the valve of opening A, B two dropwise adding tanks slowly drips material to reactor, control 70～75 DEG C of temperature of reaction, after 5.5h, B dropwise adding tank material drips off, after 6.0h, A dropwise adding tank material drips off, after insulated and stirred 1h, underpressure distillation is also collected solvent acetone 8.40Kg, to adding in reactor in the 45%NaOH of 4.28Kg and 7.6Kg technique soft water and after 1.5h, send micronizer mill to pulverize to obtain white powder finished product, be labeled as Y-5, the weight-average molecular weight of surveying through GPC is 8701g/mol.
Embodiment 6
Apply above-mentioned synthetic dispersion agent product, in the situation that other auxiliary agent kinds are identical with consumption, prepared 70% imidacloprid water dispersible granule (fluidized bed granulation) and 500g/L G-30027 water suspending agent in laboratory.Initial dispersion performance and the dispersion stabilization of evaluating dispersion agent, the consumption of dispersion agent in formula is between 4%～6%.Dispersed and cold heat storage stability as shown in Table 1 and Table 2.Experimental result shows, this dispersion agent as dispersion agent, is a kind of good novel dispersant in WDG and SC formulation.
The applicating evaluating of table 1 embodiment dispersion agent in 70% imidacloprid water dispersible granule formula
| Dispersion agent | Y-1 | Y-2 | Y-3 | Y-4 | Y-5 |
| Initial suspensibility % | 92.2 | 90.7 | 90.3 | 93.5 | 86.2 |
| Suspensibility %(54 ± 2 DEG C, 14 days) | 90.8 | 89.8 | 81.6 | 92.8 | 83.2 |
| Suspensibility %(-5 ± 2 DEG C, 14 days) | 90.4 | 89.9 | 82.4 | 92.8 | 82.6 |
The applicating evaluating of table 2 embodiment dispersion agent in 500g/L G-30027 water suspending agent formula
| Dispersion agent | Y-1 | Y-2 | Y-3 | Y-4 | Y-5 |
| Dispersed | Excellent | Excellent | Good | Excellent | Poor |
| Initial suspensibility % | 90.1 | 92.7 | 85.6 | 93.0 | 72.7 |
| Suspensibility %(54 ± 2 DEG C, 14 days) | 91.8 | 89.8 | 82.6 | 90.1 | 69.3 |
| Suspensibility %(-5 ± 2 DEG C, 14 days) | 90.8 | 89.9 | 83.4 | 90.5 | 67.9 |
Claims (13)
1. the preparation method of a dispersion agent, the steps include: under nitrogen atmosphere, lipophilicity monomer (A), functional absorption monomer (B), hydrophilic monomer (C) in corresponding solvent, carry out Raolical polymerizable after causing with molecular weight regulator by initiator; After Raolical polymerizable finishes, except desolventizing, regulate pH=7.0 ~ 10.0 with mineral alkali, make dispersion agent;
Described lipophilicity monomer (A) is selected from least one in alicyclic ring same clan monomer, phenyl ring class monomer, heterocyclic vinyl monomer; Described functional absorption monomer (B) is selected from the one of following substances: methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, N-vinyl morpholine, vinyl pyridine; The vinyl compound of described hydrophilic monomer (C) for containing acid, acid anhydrides or sulfonic acid group;
Described lipophilicity monomer (A) and the total mass of functional absorption monomer (B) account for the 30-65% of lipophilicity monomer (A), functional absorption monomer (B), hydrophilic monomer (C) three monomer total mass.
2. the preparation method of a kind of dispersion agent according to claim 1, is characterized in that: described Raolical polymerizable is that dropwise reaction mode is carried out, and temperature of reaction is 65 ~ 80 DEG C.
3. the preparation method of a kind of dispersion agent according to claim 1, is characterized in that: described molecular weight regulator is mercaptoethanol, Thiovanic acid, alkyl sulfhydryl; Described molecular weight regulator consumption accounts for 0.1%-1% of lipophilicity monomer (A), functional absorption monomer (B), hydrophilic monomer (C) three monomer total mass.
4. according to the preparation method of a kind of dispersion agent described in 1 to 3 arbitrary claim, it is characterized in that: described lipophilicity monomer (A) is selected from the one in following substances: vinyl pentamethylene, vinyl cyclohexane, vinyl naphthalene, vinylbenzene, alpha-methyl styrene, limonene, norbornylene, beta-pinene.
5. the preparation method of a kind of dispersion agent according to claim 4, is characterized in that: described lipophilicity monomer (A) is selected from the one in following substances: vinyl pentamethylene, vinyl cyclohexane, vinylbenzene, alpha-methyl styrene, limonene, vinyl naphthalene.
6. according to the preparation method of a kind of dispersion agent described in 1 to 3 arbitrary claim, it is characterized in that: described hydrophilic monomer (C) is selected from the one of following substances: vinylformic acid, methacrylic acid, toxilic acid, maleic anhydride, fumaric acid, myristic acid, vinyl phosphoric acid, Sodium styrene sulfonate, sodium vinyl sulfonate.
7. the preparation method of a kind of dispersion agent according to claim 6, is characterized in that: described hydrophilic monomer (C) is selected from the one of following substances: methacrylic acid, toxilic acid, maleic anhydride, vinyl phosphoric acid.
8. according to the preparation method of a kind of dispersion agent described in 1 to 3 arbitrary claim, it is characterized in that: described solvent is aromatic hydrocarbon solvent or ketones solvent.
9. the preparation method of a kind of dispersion agent according to claim 8, is characterized in that: described ketones solvent is selected from the one in following solvents: acetone, butanone, methyl ethyl ketone, pimelinketone.
10. according to the preparation method of a kind of dispersion agent described in 1 to 3 arbitrary claim, it is characterized in that: described initiator is superoxide or azo compound; Described initiator amount accounts for 0.5%-3% of lipophilicity monomer (A), functional absorption monomer (B), hydrophilic monomer (C) three monomer total mass.
The preparation method of 11. a kind of dispersion agents according to claim 10, is characterized in that: described initiator is hydrogen peroxide, benzoyl peroxide, dilauroyl peroxide, peroxidized t-butyl perbenzoate, Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile).
The preparation method of 12. a kind of dispersion agents according to claim 11, is characterized in that: described initiator is benzoyl peroxide, peroxidized t-butyl perbenzoate or Diisopropyl azodicarboxylate.
The preparation method of 13. a kind of dispersion agents according to claim 1, is characterized in that: described mineral alkali is sodium hydroxide, potassium hydroxide or ammoniacal liquor.
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| CN104211195B (en) * | 2014-09-15 | 2016-01-06 | 山东天庆科技发展有限公司 | There is composite water disposal agent of scale inhibitor germicidal action and preparation method thereof |
| CN106031855A (en) * | 2015-03-19 | 2016-10-19 | 托贾（上海）高分子材料有限公司 | Preparation and applications of carboxylate binary copolymer dispersing agents |
| WO2018107033A1 (en) * | 2016-12-09 | 2018-06-14 | Lubrizol Advanced Materials, Inc. | Aliphatic ceramic dispersant obtained by reaction of pibsa with non-polymeric amino ether/alcohol |
| CN109503776A (en) * | 2018-12-03 | 2019-03-22 | 广东科隆智谷新材料股份有限公司 | A kind of preparation method of polyocarboxy acid type ceramic dispersants |
| CN111003971A (en) * | 2019-09-30 | 2020-04-14 | 上海晶阳商品混凝土有限公司 | Low-slump loss concrete and preparation method thereof |
| CN111057176B (en) * | 2019-12-29 | 2020-12-04 | 权冉(银川)科技有限公司 | Tracer agent suitable for complex geological environment energy development and interpretation method thereof |
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| CN101391194A (en) * | 2008-10-27 | 2009-03-25 | 上海师范大学 | Terpolymer dispersants and preparation technique and use thereof |
| CN102585082A (en) * | 2012-01-17 | 2012-07-18 | 上海师范大学 | Methacrylic acid-styrene-hydroxyethyl acrylate copolymer dispersant and preparation method and application thereof |
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| CN101391194A (en) * | 2008-10-27 | 2009-03-25 | 上海师范大学 | Terpolymer dispersants and preparation technique and use thereof |
| CN102585082A (en) * | 2012-01-17 | 2012-07-18 | 上海师范大学 | Methacrylic acid-styrene-hydroxyethyl acrylate copolymer dispersant and preparation method and application thereof |
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Inventor after: Zhang Bo Inventor before: Duan Haibao Inventor before: Liu Guangxiang Inventor before: Zhou Hong Inventor before: Yu Panpan Inventor before: Yu Weihua Inventor before: Yuan Guojun Inventor before: Zhao Shunping |
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Effective date of registration: 20170303 Address after: 510000 Tianhe District, Guangzhou, Dongpu, No. two, No. 6 road, room 5, room, 7, 7-207 Patentee after: Guangzhou Zhen Tai Chemical Technology Co., Ltd. Address before: Hongjing road in Nanjing city of Jiangsu province in 211171 No. 3601 Nanjing Xiaozhuang University Patentee before: Duan Haibao |
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| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140625 Termination date: 20210326 |